Vinyl chloride polymers plasticized with morpholides



y 28, 1[968 F. c. MAGNE ETAL 3,385,813

VINYL CHLORIDE POLYMERS PLASTICIZED WITH MORPHOLIDES Filed July 20, 1966FRANK C. MAGNE EVALD 1.. SKAU R0 BERT R.MOD

INVENTORS ATTORNEY United States Patent AEBSTRA ST 0F THE DESCLQSUREVinyl chloride polymers and vinyl chloride-vinyl acetate copolymers areplasticized with compatible, solvent-type, primary plasticizerscomprising mixed morpholides of long chain saturated and unsaturatedfatty acids or their epoxidized derivatives. T he fatty acids are 16 to22 carbon atoms found in natural glycerides. Compatibility with thevinyl polymers is achieved through careful selection of the proportionsof saturated, monounsaturated, polyunsaturated, and epoxidized fattyacids from which the mixed morpholides are produced.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the World for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a continuation-in-part of Ser. No. 334,685 filedDecember 10, 1963, which was a division of Ser. No. 166,742, filed Jan.15, 1962, now United States Patent No. 3,219,664.

This invention relates to vinyl chloride polymers plasticized withcertain unique mixed morpholides. More particularly, the inventionprovides plastic compositions of vinyl chloride polymers and vinylchloride-vinyl acetate copolymers plasticized with the morpholides ofmixtures of long chain saturated and unsaturated fatty acids and theepoxy derivatives thereof that can reproducibly be produced from thefatty acids containing from 16 to 22 carbon atoms found in naturalglycerides. These mixed morpholides are efficient primary solventplasticizers exhibiting good compatibility with the polymers andcopolymers of vinyl chloride.

A morpholide of an acid is an amide of the acid in which the amidonitrogen atom is a nitrogen atom of a morpholine ring. Prior workershave produced the morpholides and other amides of various individualfatty acids and mixtures of fatty acids. Many of the fatty acid amidesheretofore produced, e.g., those disclosed in US. Patents 1,936,854;2,339,056; and 2,380,925; are solvent plasticizers for hydrophilic vinylresins, such as the polyvinyl acetal resins.

A compound which is a solvent plasticizer for, and thus is compatiblewith, a hydrophilic vinyl resin such as a polyvinyl acetal resin,exhibits only a very limited compatibility with a hydrophobic vinylresin such as a polyvinyl chloride. If a resin is plasticized with acompound with which it has only a limited compatibility the plasticizersoon exudes or migrates to the surface unless the "ice plasticizer isused in limited amount, or is used in conjunction with a mutual solvent,to obtain adequate compatibility.

As might be expected from the known compatibility of various morpholidesof fatty acids with the polyvinyl acetals, the morpholide mixtures fromglyceride oil acids such as cottonseed oil acids or peanut oil acids,are highly incompatible with polymers of vinyl chloride, even when usedas a secondary plasticizer with an equal amount of compatibleplasticizer. Similarly, the morpholide of palmitic acid and themorpholide of stearic acid have been found to be highly incompatiblewhen used as plasticizers for vinyl chloride resins, exhibitingmigration to the surface within 36 hours. However, in accordance withthe present invention, it has been discovered that the morpholides ofthe unique mixtures of fatty acids, defined below, exhibit goodcompatibility with vinyl chloride resins.

The term vinyl chloride resins is used throughout the specification andclaims to refer to polymers and copolymcrs of monomers containing vinylchloride in a predominant proportion in parts by weight. Terms such asgood compatibility, compatible, and compatible plasticizers in referenceto plasticizers for vinyl chloride resins are used throughout thespecification to refer to plasticizers which show no signs of exudationor migration to the surface for at least days when the plasticizer ispresent in the proportion of about parts per parts by Weight of vinylchloride resin.

The primary object of the present invention is to provide plasticcompositions containing mixed morpholides which are good primary solventplasticizers for vinyl chloride resins, and which are plasticizers thatcan be economically be produced from fatty acids obtainable fromglyceridic oils and fats.

In order that the invention be readily understood, reference is made tothe following description and to the accompanying drawing, the singlefigure of which constitutes a ternary diagram of the morpholides ofmixed fatty acids defining compositions according to the invention.

The mixed morpholides provided by this invention exhibit goodcompatibility with polymers and copolymers of monomers predominating invinyl chloride, such as polyvinyl chloride, and the vinyl chloride-vinylacetate copolymers predominating in vinyl chloride. They may be employedas plasticizers in proportions of from 10 to about 70 parts by weightper 100 parts by weight of polymer. Their plasticizing eiiiciency ishigh and the resulting plasticized resins have good thermal and lightstability, good low-temperature properties, and a low volatility loss.

As disclosed in US. Patent No. 2,863,845, the morpholides of mixedsaturated and unsaturated vegetable oil fatty acids are good compatibleplasticizers for vinyl chloride resins when the proportions of saturatedacids, monoolefiuic acids, polyolefinic acids, and epoxidized fattyacids in the mixed acids are such that S-t-M-t-P-l-E is about from 100and M +P+E is less than about l/ 10. In the foregoing fractions,

The value of E in the above fractions is zero when no epoxidized fattyacids are present. The term epoxidized fatty acids is used to designateC to C alkanoic and alkenoic acids containing at least one epoxy group.Such acids are produced by the epoxidation of at least one olefinicgroup of an unsaturated fatty acid.

In US. Patent No. 3,006,111, it was further disclosed that themorpholide mixtures obtained by reacting morpholine with mixtures of thefatty acids which occur in selectively hydrogenated cottonseed oil, saidmorpholide mixtures containing a proportion of saturated,monounsaturated, and polyunsaturated acyls; i.e., acyls obtainable fromselectively hydrogenated cottonseed oil, such that the acyls areequivalent to a mixture of acids in which S/S-i-M-l-P is about 25/100and P/M-l-P is less than 1/ are good compatible plasticizers for vinylchloride resins.

We have now made the surprising discovery that mixtures of morpholidesof vegetable oil fatty acids containing a proportion of saturated,monounsaturated, and polyunsaturated acyls of from 16 to 22 carbon atomssuch that the acyl mixture is equivalent to a mixture of acids in whichP/ M +P is much larger than l/ 10 are compatible plasticizers for vinylresins provided the value of S/S-i-M-l-P lies Within a specified rangewhich depends on the value of P/M-i-P and provided also that thesaturated acyls present in the morpholide mixture are predominantlysaturated acyls containing from 12 to 18 carbon atoms and that thepercentage of saturated acyls containing 18 or more carbon atoms in themorpholide mixture amounts to less than about 17% of all the acyls inthe morpholide mixture. For example, as can be seen from the examplesand the drawing (in which, drawing, as described below, all compositionswith in the approximate boundaries of area Mfgc are compatible),mixtures of saturated, monounsaturated, and polyunsaturated morpholidesfor which P/ M +P=25/ 100 (represented by the compositions along thestraight line joining x and S) are compatible only between i and [1;that is, only if the value of S/S+M+P lies between about /100 and 60/100and provided also that the saturated acyls present in the morpholidemixture are predominantly saturated acyles containing from 12 to 18carbon atoms, and that the percentage of saturated acyls containing 18or more carbon atoms in the morpholide mixture amounts to less thanabout 17% of all the acyls in the morpholide. This is surprising since,as is obvious from the drawing, such compatible plasticizing mixturescan be prepared by mixing two incompatible plasticizers; i.e., forexample, by mixing equal weights of the compositions represented by Sand at, each of which is incompatible, or in general, by mixing thecompositions represented by S and x in any proportion between about 1and 6 parts by weight of x to 4 parts by weight of S.

Similarly we have also discovered that mixtures of morpholides ofvegetable oil fatty acids in which S/S-i-M-l-P is much larger than /100are compatible vinyl plasticizers provided the ratio P/M-l-P lies withina specified range of values and provided also that the saturated acylspresent in the morpholide mixture are predominantly saturated acylscontaining from 12 to 18 carbon atoms and that the percentage ofsaturated acyls containing 18 or more carbon atoms in the morpholidemixture amounts to less than about 17% of all the acyls in themorpholide mixture. This is surprising since it shows, as can be seenfrom the drawing that compatible plasticizers represented by thecompositions within area Mfgc can be obtained by mixing (in appropriateproportions) two incompatible plasticizers, e.g., those represented bycompositions in areas Mrfa and cgS, respectively.

We have also discovered that mixtures of the morpholides of saturated,polyunsaturated, and epoxidized fatty acids in which S/S+M+P+E is muchlarger than 9/ and P/M+P+E is much larger than 1/10 but which arecompatible vinyl chloride resin plasticizers can be made by mixing twoincompatible morpholide mixtures, provided that the saturated acylspresent in the morpholide mixture are predominantly saturated acylscontaining from 12 to 18 carbon atoms, and that the percentage ofsaturated acyls containing 18 or more carbon atoms in the morpholidemixture amounts to less than about 17% of all the acyls in themorpholide mixture. For example, the composition represented by Example43, for which P/P+E=about 35/100 and the composition represented byExample 40, for which S/S-l-P-f-E =a-bout 75/100 are individuallyincompatible, but a mixture of equal parts of these compositions(Example 46), for which E/E+S=54/100 and E/P+E:72/l00 is compatible.

The mixed morpholides of this invention comprise the morpholides ofmixed saturated and unsaturated fatty acids, in which mixture of acids,the weight proportions of saturated acids (S), monoolefinic acids (M),and polyolefinic acids (P), are such that the following conditions aresatisfied: 1) that S/S-i-P is greater than about 50/100 (i.e., that thecomposition lies within area MES in the drawing), (2) that M/S-l-M-l-Pis greater than about 30/100 (i.e., that the composition lies withinarea M), and (3) that P/M-l-P is less than about 40/100 (i.e., that thecomposition lies within area MaS), excluding those mixtures wherein LnS+M+P is about from 1/100 to 9/100 and i M+P is less than about 1/ 10(i.e., excluding those compositions lying Within the approximate areaMrk of the draw ing) and excluding the morpholides of selectivelyhydrogenated cottonseed oil fatty acids, the selective hydrogenationbeing performed under conditions which result in reducing the proportionof polyolefinic acyls in the mixture by converting the polyolefinicacyls to monoolefinic acyls without substantially increasing theproportion of saturated acyls in the mixture, said morpholide mixtureconsisting of the morpholides of monoolefinic fatty acids (M),polyolefinic fatty acids (P), and saturated fatty acids (S), saidsaturated fatty acids (S) being present in an amount ranging from about23/100 to 28/ 100, and in which morpholide mixture the proportion of thepolyolefinic fatty acyls based on the total unsaturated acyls is suchthat is less than 1/10 by weight (i.e., excluding those compositionslying approximately on the line ny of the drawing); provided also thatthe saturated acyls present in the morpholide mixture are predominantlysaturated acyls containing from 12 to 18 carbon atoms, and that thepercentage of saturated acyls containing 18 or more carbon atoms in themorpholide mixture amounts to less than about 17% of all the acyls inthe morpholide mixture. Thus, the mixed morpholides of this inventioncomprise compositions represented by all compositions within the areakrfgc in the drawing except along ny; that is, the area which is commonto the 'areas MeS, Mbc, and

MaS, excluding those within the area Mrk and along line ny.

The morpholides of this invention also include the morpholides ofepoxidized fatty acids. They also include the morpholides of mixtures ofepoxidized fatty acids with saturated acids and/or polyunsaturated fattyacids in which mixtures of acids, the weight proportions of saturatedacids (S), epoxidized acids (E), and polyunsaturated acids (P), are suchthat the following conditions are satisfied: (1) that E/S+E is greaterthan about 50/100; (2) that E/P-t-E is greater than about 70/100; and(3) that the saturated acids present in the mixture of 'acids arepredominantly saturated acids containing from 12 to 18 carbon atoms andthe percentage of saturated acids containing 18 or more carbon atoms insaid mixture of acids is less than about 17% of all the acids in themixture.

While the morpholides of this invention can be produccd in 'a variety ofways, they are preferably produced by reacting the mixed acids withmorpholine. The mixed acids are preferably produced by saponifying anatural glyceride, acidifying the resulting salts and, if necessary,adjusting the composition of the resulting acid mixture so as to obtaina suitable composition which when reacted with morpholine will result ina compatible plasticizer (l) by known procedures for reducing theproportion of saturated acyls such as fractional crystallization ordistillation, and/or (2) converting polyunsaturated 'acyls tomonounsaturated acyls, epoxyalkenoic acyls or epoxyalkanoic acylsthecorresponding morpholides of which are themselves compatibleplasticizerssuch as by hydrogenation, halogenation, formylation,dimerization, epoxidation, etc., and/or (3) by admixing with other fattyacid mixtures and/ or with pure fatty acids. Alternatively, thefractionation, hydrogenation, epoxidation or mixing, etc., may beperformed on the materials separately or combined which are capable ofyielding the desired acid compositon or on the corresponding morpholidesor mixed morpholides. In general, it is usually preferred to performepoxidation at the morpholide stage.

The necessary adjustment can readily be deduced from the drawing andfrom a knowledge of the proportions of S, M, and P acyls in the givenmixture as determined by standard analytical procedures. For example,consider a mixture of vegetable oil fatty acids in which the weightproportions are such that S/S+P is about 35/ 100; P/M+P is about 65/100;M/S-l-M-l-P is about /100; and in which the predominant saturated fattyacid is the C acid with very small amounts of the C and C acids. Thedrawing shows that the mixed morpholides made from this mixture(represented approximately by w in the drawing) would be incompatible.The drawing also shows that this mixture of fatty acids can be readilyconverted to a suitable mixture of acids (i.e., to a compositionrepresented by points within area krfgc), which when reacted withmorpholine will result in a compatible plasticizer; for example, byconverting some or all of the polyunsaturated acyls to monounsaturatedacyls by such procedures as hydrogenation, halogenation, formylation,dimerization, maleination, etc., so that S/S-i-P is greater than about50/100, M/S+M+P is greater than about /100, and P/-M+P is less thanabout /100.

The composition of the morpholide mixtures of this invention whichcontain no epoxidized acyls are represented by all compositions withinthe area krfgc in the drawing; that is, within the area boundedapproximately by kr, rf, fg, and gc. The boundaries kr, rf, fg, and goare only approximate. Thus the composition of Example 10 which lies nearthe boundary outside this area (the open circle just below line gc) wascompatible. Slightly incompatible compositions lying close to butoutside the bound aries kr, rf, g and gc and even less compatiblecompositions may be used satisfactorily as primary plasticizers inpolyvinyl chloride resin formulations containing lower percentages ofplasticizer and/ or as secondary plasticizers admixed with a suitablecompatibilizing plasticizer such as the morpholide of epoxidized fatty'acids or compatible mixtures of the morpholides of epoxidized fattyacids and/or monounsaturated fatty acids and/0r polyunsaturated fattyacids and/or saturated fatty acids. Similarly incompatible morpholidemixtures containing the morpholides of epoxidized fatty acids can beused as secondary plasticizers with compatible morpholide compositionswhich lie within the area krfgc in the drawing.

The proportion of the saturated fatty acyls having 18 or more carbonatoms in the chain which can be present in the saturated acyl fractionwithout causing incompatability will vary with the overall compositionof the morpholide mixture particularly the relative proportions ofsaturated, monounsaturated, and polyunsaturated acyls present in themixture. It can be determined for a given overall composition byevaluating the performance of a series of samples which differ only inthe proportion of the C or longer-chain saturated fatty acyls in thesaturated fatty acyls present.

We have also discovered that the morpholides of epoxidized fatty acids,i.e., of C to C alkanoic or alkenoic acids containing at least one epoxygroup, are compatible, highly efiicient, primary plasticizers for vinylchloride resins and impart to the plasti-cized resin a high degree ofstability against heat and light. They are efficient stabilizers forvinyl chloride resins. We have also discovered that morpholide mixturessuch as can be made by mixing even as much as about one part of themorpholide of palmitic acid with one part of the morpholide ofepoxidized fatty acids or by mixing as much as about 3 parts of themorpholide of polyunsaturated fatty acids with 7 parts of the morpholideof epoxidized fatty acids are 'also found to be compatible vinylchloride resin plastizers and have the advantage that the plasticizedresin has increased thermal stability.

Morpholide mixtures which can be prepared by mixing in any proportionany of the compatible morpholide compositions within the 'area krfgc inthe drawing with either the morpholides of epoxidized fatty acids orwith any mixture of morpholides of fatty acids containing the morpholideof epoxidized fatty acids which mixture of morpholides is itself acompatible vinyl chloride plasticizer are also compatible vinyl chlorideplasticizers imparting good thermal stability to the resin. In makingsuch compatible morpholide mixtures the morpholides of epoxidized fattyacids may be introduced by addition or they may be formed in situ; forexample, by epoxidizing some of the morpholides of the monounsaturatedor polyunsaturated fatty acids in a given morpholide mixture.

The following examples numbered 1 through 46, the data for which arelisted singly in tabular form but which may be considered individuallyor in related groups for discussion purposes, will demonstrate severalof the manifold expressions of our invention.

Various morpholide mixtures were tested as plasticizers for a vinylchloride-vinyl acetate (5) copolymer resin in a standard formulationcomprising: 63.5% of resin, 35% plasticizer, 0.5% stearic acid, and 1.0%basic lead carbonate. This formulation for each morpholide sample wasmilled, molded, and tested. In all examples, the sample was rated asincompatible if the molded stock showed any evidence of exudation ormigration to the surface during a shelf storage of 30' days.

The morpholide mixtures used in Examples 1 to 19 were ternarycompositions prepared by mixing appropriate proportions of themorpholide of oleic acid, the morpholide of linoleic acid, and themorpholide of palmitic acid. The approximate compositions and theresults of the compatibility test for these samples are given in Table Iand plotted as points in the ternary weight-composition diagram in thedrawing. In the drawing compatible morpholide mixtures are representatedby open circles and incompatible mixtures by black circles. In TableTABLE I M, S, and P, represent the weight percent of the morpholides ofmonoolefinic, saturated and polyolefinic fatty acids, respectively,comprising the morpholide mixture, in which morpholide mixture, thesaturated acyls containing 18 or more carbon atoms amount to less thanabout 17% Ex- Wt. Percent p or holid mixture. ample 1\ 1/s+1\1+1 PIM+PSIS+P bility 1 of an the acy 1s m the p e No. 11 s P 00.5 33.1 1.301/100 351 8 51.2 47.7 1.1 51100 1 73.0 14.5 0.3 W100 3/100 8 10 TABLEII 71.4 10.2 0.3 1100 12100 7 1 E W Percent Com P 30.7 0.3 0.5 31 10011/100 51 100 0 M 37.2 01.0 0.3 37/100 2/100 00/100 C 1 3 M Mls+M+PS/sl'P 3 2.1/13 303 3 5.5 42. 1-.3 0100 35.1 43.2 21.5 35/100 33/10007/100 0 2g 22 g Zgflgg 8 20.3 57.4 10.1 20 100 33 100 73 100 8 22IIIII00.4 7.0 23.0 00/100 100 25 100 1 22 C Q 23. 72.2 10.3 11.5 72/10014/100 50 100 0 70.0 11.2 13.3 70 100 21/100 37/100 1 70.0 15.0 15.070/100 13/100 50/100 0 lo companble' I mcompmbm' 43.4 30.0 20.0 43 10032 100 04 100 0 45.3 40.1 14.0 100 24/100 73 100 0 40.5 30.0 20.5 41/10042/100 /100 I 22:8 2:2 8:2 20 The physical properties of the v nylchloride-vinyl acetate copolymer resin plast1c1zed with the morpholidemix-- C=mPal1b1i I=mmPanb1etures of Examples 20 to 23 are shown in TableIII.

TABLE III Tensile 100% Elonga- Brittle Voln- Compati- Example No.Plasticizer, Morpholide of- Strength, Modulus, tion, Point, tilitybility 1 p.s.i. p.s.i. Percent C.

20 Animal type acids 2, 940 1,390 400 -30 0.02 O 21.-. Animal acids 2,050 1,370 300 -34 0.30 c 22 Rapeseed oil acids 3,030 1,470 400 -53 1.00I 23 Adjusted rapeseed oil acids 2,880 1, 330 300 -43 0.55 C 24Epoxyoleic acid 3, 030 1,270 300 -10 0.41 C 25 Epoxystearie acid ,850 1,300 350 -28 0. 54 C 26 Diepoxysteario acid 2, 950 1, 330 350 16 0. 49 C27. Partially epoxidized cottonseed oil a 2, 940 1, 210 400 -26 0. 73 C28 Fully epoxidized cottonseed oil acids" 2, 090 1, 310 360 -22 0. 72 OC=compatible; I=incompatible.

The sample used in Example 20 was the morpholide of a mixture of fattyacids having the following composition: 10% myristic, 43% palmitic, 9%stearic, 30% oleic, and 8% linoleic acids.

The sample used in Example 21 was the morpholide of a mixture of fattyacids having the following composition: 2% myristic, 26% palmitic, 16%stearic, 48% oleic and 8% linoleic acids.

The morpholide of rapeseed fatty acids used in Example 22 was preparedfrom the composite fatty acids which were obtained by saponification andacidification of rapeseed oil and which consisted of approximately 9.6%linolenic acid, 13.3% linoleic acid, 20.4% oleic acid, 49% erucic acid,and 7.6% saturated fatty acid. The resulting morpholide mixture, forwhich the composition was such that JVI/S+M+P=69/100, P/M+P=25/l00, and

was tested as a plasticizer for the vinyl chloride-vinyl acetate (95-5)resin and was incompatible.

The morpholide sample of Example 23 was made by adjusting thecomposition of the morpholide mixture of Example 22. The latter wasmixed with an equal part by weight of a morpholide mixture thecomposition of which was such that M/S+M+P=about 75/100,

P/M-l-P: about 0 and S/S+P=about 100/100, resulting in a final mixturefor which M/S-l-M+P=about 72/100, P/M-l-P=about 14/100 and S/S+P=about59/100. This was found to be a compatible plasticizer for the vinylchloride-vinyl acetate (95-5) copolymer resin mentioned above.

The compositional data for the morpholide mixtures of Examples 20 to 23are given in Table II in which table The corresponding data for Examples24 to 29 are given in Tables III and/or IV. For these samples, M, E, S,and P represent the approximate weight percent of morpholides ofmonoolefinic (unepoxidized), epoxidized, saturated and polyunsaturatedacids, respectively, comprising the morpholide mixtures, in whichmorpholide mixtures the saturated acyls containing 18 or more carbonatoms amount to less than about 17% of all the acyls in the morpholidemixture. The morpholide samples of Examples 27 and 28 were prepared byepoxidation of the morpholide of cottonseed oil fatty acids to anoxirane oxygen content of 2.62% and 4.07%, i.e., to an extent equivalentto that necessary to epoxidize about 50% and about respectively, of thetotal number of double bonds present.

The morpholide sample of Example 29 was prepared by mixing the properproportions of the morpholide mix ture of Example 28 and the morpholideof selectively hydrogenated cottonseed fatty acids. The plasticizedresin had a specially high degree of thermal stability.

The morpholide mixtures used in Examples 30 to 36, for which thecompatibility data are given in Table IV, were prepared by mixing theproper proportions of the morpholides of oleic acid, epoxyoleic acid,and palmitic acid.

The morpholide mixtures used in Examples 37, 38 39, 40, 41, 42, and 43were binary compositions pre pared by mixing appropriate proportions ofthe morpholide of epoxyoleic acid with either the morpholide o1 linoleicacid or with the morpholide of palmitic acid. The morpholide mixturesused in Examples 44, 45, and 46 were ternary mixtures consisting ofequal parts by weight of the mixture used in Example 40 and those usedin Examples 41, 42, and 43, respectively. The compositions and theresults of the compatibility tests for these samples are given in TableIV. The sample of Example 46 was a compatible vinyl chloride plasticizerthough it was made by mixing the samples of Examples 40 and 43 both ofwhich were incompatible.

TABLE IV Example M E s P EIE+S E/P+E Compati- No. bility oooooooooowcoo:

men

1 O=compatiblc; I=incompatible.

2 Compositions containing the morpholides of both monounsaturated fattyacids and epoxidized fatty acids, and which can be prepared by mixingappropriate proportions of two morp olidc mixtures each of which is acompatible vinyl chloride plasticizer.

3 Compositions containing the morpholides of both monounsaturated fattyacids and epoxidized fatty acids, and which can be prepared by mixingtwo morpholide mixtures each of which is an incompatible vinyl chlorideplasticizer. For example, the sample of Example 36 can be prepared bymixing equal parts by weight of two incompatible morpholide mixtures,one consisting of 25 parts of the morpholide of a monounsaturated acidand 75 parts of the morpholide of palInit-ic acid and the otherconsisting of 35 parts of the morpholide of epoxyoleic acid and 65 partsof the morpholide of palmitic acid.

\Ve claim:

1. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from to 70 parts per100 parts of resin of a plasticizer therefor, said plasticizercomprising the morpholides of a mixture of saturated and unsaturatedfatty acids of from 16 to 22 carbon atoms, said mixture of acids beingdefined by compositions falling within the area krfgc in the drawing,with the exclusion of mixtures falling on the line ny, provided that thesaturated acids present in the said mixture of fatty acids arepredominately saturated acids containing from 12 to 18 carbon atoms andthat the percentage of saturated acids containing at least 18 carbonatoms in the said mixture of acids is less than about 17% of all theacids in the mixture.

2. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts per100 parts of resin of a plasticizer therefor comprising the morpholidesof a mixture of epoxidized fatty acids and saturated fatty acidscontaining from 16 to 22 carbon atoms in which mixture of acids theweight proportions of saturated acids (S), epoxidized acids (E) are suchthat the following conditions are satisfied: 1) E/S-t-E is greater thanabout 50/100; (2) the saturated acids present in the said mixture ofacids are predominantly saturated acids containing from 12 to 18 carbonatoms; and (3) the percentage of saturated acids containing at least 18carbon atoms in said mixture of acids is less than about 17% of all theacids in the mixture.

3. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts perparts of resin of the morpholides of a mixture of epoxidized fatty acidsand polyunsaturated fatty acids containing from 16 to 22 carbon atoms inwhich mixture of acids the weight proportions of epoxidized acids (E)and polyunsaturated acids (P), are such that E/P-j-E is greater thanabout 70/ 100.

4. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts per100 parts of resin of a plasticizer therefor comprising the morpholidesof a mixture of epoxidized fatty acids, saturated fatty acids, andpolyunsaturated fatty acids containing from 16 to 22 carbon atoms inwhich mixtures of acids the weight proportions of saturated acids (S),epoxidized acids (E), and polyunsaturated acids (P), are such that thefollowing conditions are satisfied: (1) that E/S-l-E is greater thanabout 50/100; (2) that E/P-l-E is greater than about 70/100; (3) thatthe saturated acids present in the mixture of acids are predominantlysaturated acids containing from 12 to 18 carbon atoms; and (4) that thepercentage of saturated acids containing at least 18 carbon atoms insaid mixture of acids is less than about 17% of all the acids in themixture.

5. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts per100 parts of resin of a plasticizer therefor selected from the groupconsisting of the morpholides of epoxyoleic acid, epoxystearic acid, anddiepoxystearic acid.

6. The plastic composition of claim 5 wherein the plasticizer is themorpholide of epoxyoleic acid.

7. The plastic composition of claim 5 wherein the plasticizer is themorpholide of epoxystearic acid.

8. The plastic composition of claim 5 wherein the plasticizer is themorpholide of diepoxystearic acid.

9. The plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts-per100 parts of resin of a plasticizer therefor comprising the morpholidesof cottonseed oil fatty acids epoxidized to an oxirane content of 2.62%.

10. A plastic composition which is stable against exudation ofplasticizer comprising a mixture containing a vinyl chloride polymerselected from the group consisting of polyvinylchloride and a vinylchloride-vinyl acetate copolymer which contains a predominant amount ofvinyl chloride and a plasticizer therefor comprising the morpholides ofcottonseed oil fatty acids epoxidized to an oxirane content of 4.07%.

11. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from 10 to 70 parts per100 parts of resin of the morpholides of a mixture of epoxidized fattyacids, saturated fatty acids, and monounsaturated fatty acids containingfrom 16 to 22 carbon atoms, in which mixture of acids the weightproportions of saturated acids (S), epoxidized acids (E),

and monounsaturated acids (M) are such that the following conditions aresatisfied:

is less than about 50/100; (2) the saturated fatty acids present in saidmixture of acids are predominantly saturated acids containing from 12 to18 carbon atoms; and (3) the percentage of saturated acids containing atleast 18 carbon atoms in said mixture is less than about 17% of all ofthe acids in the mixture.

12. A plastic composition which is stable against exudation ofplasticizer comprising a major portion of a vinyl chloride resinouspolymer selected from the group consisting of a polyvinylchloridehomopolymer and a vinyl chloride-vinyl acetate copolymer which containsa predominant amount of vinyl chloride and about from to 70 parts per100 parts of resin of the morpholides of a mixture of epoxidized fattyacids, saturated fatty acids, and monounsaturated fatty acids containingfrom 16 to 22 carbon atoms, in which mixture of acids the Weightproportions of saturated acids (S), epoxidized acids (E), andmonounsaturated acids (M) are such that the following conditions aresatisfied:

S S+M+E is between /100 and /100;

i S+M+E is greater than 5/100; (3) the saturated acids present in saidmixture of acids are predominantly saturated acids containing from 12 to18 carbon atoms; and (4) the percentage of saturated acids containing atleast 18 carbon atoms in said mixture of fatty acids is less than about17% of all the acids in the mixture.

References Cited UNITED STATES PATENTS 2,863,845 12/1959 Magne et al260-304 3,066,111 11/1962 Magne et a1 26030.4

MORRIS LIEBMAN, Primary Examiner.

L. T. JACOBS, Assistant Examiner.

